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IC 


8953 



Bureau of Mines Information Circular/1983 




Methods for Characterizing Manganese 
Nodules and Processing Wastes 



By Benjamin W. Haynes, David C. Barron, 
Gary W. Kramer, and Stephen L. Law 




UNITED STATES DEPARTMENT OF THE INTERIOR 



Information Circular 8953 



1 

Methods for Characterizing Manganese 
Nodules and Processing Wastes 



By Benjamin W. Haynes, David C. Barron, 
Gary W. Kramer, and Stephen L. Law 




UNITED STATES DEPARTMENT OF THE INTERIOR 
James G. Watt, Secretary 

BUREAU OF MINES 
Robert C. Norton, Director 



Library of Congress Cataloging in Publication Data: 



^> 







.p 



V^''■ 



Methods for characterizing manganese nodules and 


processing wastes. 


(Information circular / Bureau of Mines ; 8953) 




Bibliography: p. 10. 




Supt. of i:)ocs, no,: I 28.27:8953. 




1. Manganese nodules— Analysis. 1. Haynes, 


Benjamin VC. 11. Se- 


ries: Information circular (United States. Bureau 


af Mines) ; 8953. 


-^WWOSOJi [QE390.2.IV135] 622s r553.4'629'0287] 83-600240 



CONTENTS 



Page 

Abstract 1 

Introduction 2 

Physical methods 2 

Compound identification methods 2 

Chemical characteristics 4 

Atomic absorption spectrophotometry 4 

Inductively coupled plasma atomic emission spectroscopy 6 

Neutron activation analysis 6 

X-ray fluorescence spectrography 6 

Ion chromatography 6 

Wet chemical methods 7 

Comparison of chemical analysis results 7 

Leaching tests 8 

EP toxicity test 8 

ASTM shake extraction test 8 

U.S. Army Corps of Engineers seawater elutriant test 9 

Results of leaching tests 9 

Conclusions 9 

References 10 



TABLES 

1 . Suggested test procedures for determining physical properties of manganese nodule 

reject waste materials 3 

2. Physical properties of pilot plant- and laboratory-generated Cuprion process tailings 3 

3. Compo.und identification and elemental analysis methods for manganese nodule 

materials 3 

4. Sources of interference in elemental determination by quantitative instrumental 

methods 5 

5. Sample dissolution and elemental analysis procedures for manganese nodule 

materials 5 

6. Ion chromatograph operating conditions for determining anions and NH4^ 7 

7. Comparison of interlaboratory analyses of manganese nodule standards 7 

8. Round-robin results for Cuprion process reject waste material, solid phase 8 

9. Round-robin results for Cuprion process reject waste material, liquid phase 8 

10. Element concentration in leachate from leaching tests on Cuprion process reject waste 

material 9 



LIST OF UNIT OF MEASURE ABBREVIATIONS USED IN THIS REPORT 



cm/s 


centimeter per second 


mUmin 


milliliter per minute 


deg 


degree 


mm 


millimeter 


°C 


degree Celsius 


mm 


minute 


g 


gram 


nm 


nanometer 


h 


hour 


pet 


percent 


pg 


microgram 


pcf 


pound per cubic foot 


pg/mL 


microgram per milliliter 


psi 


pound per square inch 


pm 


micrometer 


wt pet 


weight percent 


mL 


milliliter 







METHODS FOR CHARACTERIZING MANGANESE 
NODULES AND PROCESSING WASTES 



By Benjamin W. Haynes,^ David C. Barron,^ Gary W. Kramer,^ 
and Stephen L. Law'* 



ABSTRACT 



Analytical procedures are described for the quantitative determination of 1 6 elements (As, 
Ba, Be, Cd, Co, Cr, Cu, Fe, Mn, Mo, Nl, Pb, Sb, Se, Tl, and Zn) and 7 ionic species (NH4*, 
COa^", cr, F", NO3", P04^", SO/'), identification of major and minor mineral components, and 
measurement of physical properties associated with manganese nodules and nodule pro- 
cessing reject waste materials. 

Compound identification methods discussed include X-ray diffraction, infrared spectroscopy, 
scanning and transmission electron microscopy, selective area electron diffraction, and 
optical and reflected light microscopy. Methods for elemental analysis Include atomic 
absorption spectrophotometry, inductively coupled plasma emission spectroscopy, neu- 
tron activation analysis, fluorescent X-ray spectrography, and ion chromatography. Thermal 
gravimetric analysis, ultraviolet-visible spectrophotometry, ion specific electrodes, and stan- 
dard wet chemical procedures are briefly discussed. 

Physical properties determined In manganese nodule materials include grain size distribution, 
specific gravity, triaxlal shear, permeability, maximum density, Atterberg limits, and slurry 
density. 

The results of a round-robin analysis of an ammonia process waste material and manga- 
nese nodule standards demonstrate the applicability of the discussed methods. 

Tests discussed for the evaluation of the waste materials for disposal options include the 
Environmental Protection Agency (EPA) EP toxicity test, the ASTM shake extraction test, 
and the U.S. Army Corps of Engineers EPA seawater elutriant test. 

'Supervisory research chemist. 

^Chemist. 

^Research chemist. 

■•Research supervisor. 

Avondale Research Center, Bureau of Mines, Avondale, MD. 



INTRODUCTION 



Deep seabed mining for manganese nodules, including the 
processing of nodules to recover value metals, raises a variety 
of environmental, social, and economic considerations. To 
address the waste management aspects of the recovery of 
value metals from nodules, the National Oceanic and Atmo- 
spheric Administration (NOAA) of the Department of Commerce, 
the Environmental Protection Agency (EPA), and the Depart- 
ment of the interior's Bureau of Mines and Fish and Wildlife 
Service, after consultation with industry, academia, and other 
concerned interests, entered a multiyear cooperative research 
program which has as its overall objective: 

"To provide information needed by Federal and State 
agencies in preparation for receipt of industry's commer- 
cial waste management plans." 

The NOAA-funded research conducted by the Bureau of 
Mines has the objective of obtaining a "first-order chemical 
and physical characterization of rejects from the types of 
manganese nodule processing techniques representative of 
those being developed by industry." Three reports have been 
published since commencement of this research that delin- 
eate mineralogical and elemental composition of Pacific man- 
ganese nodules (16),^ five potential process flowsheets for 
first-generation plants (17), and prediction of the compositions 
of the reject waste materials from the five potential processes 
(75) using information obtained in the first two reports. The five 
processes considered feasible for first-generation nodule pro- 
cessing are as follows (7,77): 

1 . Gas reduction and ammoniacal leach. 

2. Cuprion ammoniacal leach. 

3. High-temperature and high-pressure sulfuric acid leach. 

4. Reduction and hydrochloric acid leach. 

5. Smelting and sulfuric acid leach. 

In order to assess any potential environmental impact of 
waste disposal from manganese nodule processing, accurate 
and precise analytical methods are essential. Because this 
industry is still in the developmental stage, actual waste materi- 



als are not available, and the direct applicability of commonly 
used analytical methods was uncertain. The combination of 
high manganese and high iron content is unique to these 
materials, and interferences will result in incorrect data unless 
precautions are taken. 

This report outlines methods that Bureau of Mines experi- 
ence has indicated are applicable to the characterization of 
nodule feed materials and the reject waste materials from all 
five potential processes. The report is divided into five sections: 
methods for determining physical properties, methods for com- 
pound identification, methods for determining chemical 
characteristics, interlaboratory comparisons of results, and 
leach tests for hazardous waste and ocean disposal assessment. 

The chemical characteristics section discusses the determi- 
nation of elements of potential economic and/or environmen- 
tal interest and anion or cation combining species. Elements 
of interest are As, Ba, Be, Cd, Cr, Co, Cu, Fe, Mn, Mo, Ni, Pb, 
Sb, Se, Tl, and Zn (75). Silver and mercury are not specifically 
addressed in this report as their levels in nodules are too low to 
warrant environmental concern (75-76). Ions of interest include 
ammonium, carbonate, chloride, flouride, nitrate, phosphate, 
and sulfate. 

The various methodologies for testing physical properties 
incorporate standard ASTM and soil mechanics procedures. 
Analysis of liquid and solid phase components for chemical 
characteristics involve the use of atomic absorption spectro- 
photometry (AAS), inductively coupled plasma spectroscopy 
(ICP), ion chromatography (IC), X-ray fluorescence (XRF), X-ray 
diffraction (XRD), and/or wet chemical procedures. Parame- 
ters such as pH, reduction-oxidation potential, and chemical 
oxygen demand may also need to be determined. Modifica- 
tions of these basic methods and the use of other methods 
may be required for specific needs of different laboratories. 

The procedures and methods presented in this report are 
not to be considered as proposed standard methods or as the 
only methods suitable for characterization of these types of 
materials. Attention has been given to methods that are capa- 
ble of multielement analysis, thereby reducing the amount of 
sample and the time required for analyses. 



PHYSICAL METHODS 



Physical characteristics are determined by the application 
of ASTM methods outlined for soils and rock testing (3). The 
test procedures listed in table 1 have been successfully applied 
to coal refuse by the Bureau of Mines (6). The same test 
procedures were used to determine the physical characteris- 
tics of tailings generated in pilot-plant and laboratory operations, 
and the results are presented in table 2. The agreement between 



results of the two types of tailings in table 2 demonstrates the 
ability to simulate the pilot-plant physical characteristics on 
the laboratory scale. However, these results may not be typi- 
cal of tailings that may be produced in a full-scale plant because 
optimization of all processing parameters is not achievable on 
a pilot-plant or laboratory scale. 



COMPOUND IDENTIFICATION METHODS 



Identification of the various compounds present in nodule 
reject waste materials allows a preliminary evaluation of the 
wastes' environmental impact. An element present in one 
chemical form may be environmentally inert, whereas a more 

^Italicized numbers in parentheses refer to Items in the list of references at the 
end of this report. 



chemically active form of the element may pose problems if 
disposed of improperly. However, this identification is inher- 
ently difficult because of the poorly crystalline, fine-grained, or 
amorphous nature of the minerals in manganese nodules and 
their tailings. Methods, such as XRD, optical microscopy, 
infrared spectroscopy, thermal analysis, and scanning and 
transmission electron microscopy, are available to identify 



Table 1. — Suggested test procedures for determining physical 
properties of manganese nodule reject waste materials 

Property Procedure' 

Grain size distributions: 

Plus 200 mesh ASTM D422-63. 

Minus 200 mesh Allen (1). 

Specific gravity ASTM D854-58. 

Triaxial shear ASTM D2850-70. 

Permeability ASTM 02434-68.= 

Maximum density ASTM D698-78. 

Minimum density ASTM D2049-69. 

Atterberg limits: 

Liquid ASTM D423-66. 

Plastic ASTM D424-59 

Soil class ASTM D2487-69. 

Slurry density ASTM D2216-71. 



ASTM tests are found in reference 3. 
■ Using Bureau of Reclamation Earth Manual Procedure E13. 



Table 2. — Physical properties of pilot plant- and laboratory- 
generated Cuprion process tailings 



Parameter 


Pilot 
plant 


Labora- 
tory 


Grain size distribution, \xm: 
1 00 pet pass 


74 

6 

1 

'3.19 

38 

5 
8.46 
90.1 

45 
41.2 
3 ML 
41.8 


600 


50 pet pass 


13 


pet pass 


1 


Specific gravity 


3 10 


Triaxial shear: 

Friction angle deg . . 

Cohesion psi. . 

Permeability^ 1 0~^ cm/s . . 

Maximum density pcf . . 

Atterberg limits: 

Liquid pet. . 

Plastic pet. . 

Soil class ... 


38.5 

4 

6.7 

92.5 

42.1 
34.4 
^ML 


Slurry density pet solids. . 


31 1 







' Dry solids. 



■ At 95 pet maximum density. 



' Lean silt. 



major and minor compounds. Table 3 includes a brief sketch 
of each of these methods along with the methods primarily 
used for elemental and anion determinations discussed in the 
next section. 

XRD is the conventional technique used to identify and 
sometimes quantify major and minor crystalline compounds. 
However, in the iron and manganese matrix of manganese 
nodules, compounds that are present at less than 5 wt pet 
and/or are extremely fine grained, generally cannot be identi- 
fied by this method. Many of the minerals present in nodules 
(76) are very poorly crystalline, and often amorphous, given 
only a diffuse XRD pattern. The reject waste materials from 
manganese nodule processing are also relatively fine grained 
but do show better crystallinity and thus better diffraction 
patterns than nodules. The major and minor components such 
as manganese carbonate, manganese oxides, silica, clays, 
and feldspars can be determined. Positive association of trace 



elements with specific compounds is virtually impossible by 
this method. 

Identification of compounds in single grains requires the use 
of the transmission electron microscope (TEM) using selec- 
tive area electron diffraction (SAED) (30). This technique uses 
very small samples and applies to single particles. Quantifica- 
tion on this scale is impractical because of the lack of appropri- 
ate standards for manganese nodule materials. 

Infrared spectroscopy (IR) is useful for the mineralogical 
analyses of manganese nodules, which cannot be performed 
by XRD {22-23). For example, it eliminates the ambiguity fre- 
quently caused in XRD by silicate components, such as the 
confusion of kaolinite and birnessite (23). Being sensitive to 
short-range order, IR provides mineralogical information on 
the disordered and fine-particulate phases that cannot be 
studied by XRD (22). However, because IR is not a primary 
structural technique like XRD, it is necessary to calibrate it 



Table 3. — Compound identification and elemental analysis methods for manganese nodule materials 



Atomic absorption spectroscopy: 

Application — Quantitative determination of a specific element, especially 
minor and trace concentrations. 

Principle — Absorption of atomic resonance line proportional to the con- 
centration of the specific element. 

Limitations — Usually not applicable to nonmetals. Metals are determined 
individually and not simultaneously. 
Atomic emission spectroscopy: 

Application — General qualitative and semiquantitative survey of all metallic 
elements. 

Principle — Light emission from excited electronic states of atoms propor- 
tional to concentration. 

Limitation — Poor for detecting volatile elements. Quantitative determina- 
tions are difficult. 
Chemical reaction methods (classical analysis): 

Application — Variety of specialized quantitative applications. 

Principle — Stoichiometry of chemical reactions. 

Limitations — Time consuming, interferences often a problem. 
Electron microscopy and microanalysis (SEM, TEM, and probe): 

Application — Morphological information and elemental composition of fine 
particles. 

Principle — A focused beam of electrons gives rise to secondary, bacl<- 
scattered, reflected, or transmitted electrons for morphological informa- 
tion, and X-rays for elemental information. 

Limitations — Sample must be small enough to fit in the sample chamber. 
Less than about 6-mm square maximum area is viewed by SEM, less than 
1.5-mm square area for TEM, and about 50-mm square area for an 
electron probe. 



Inductively coupled plasma: 
Application — Minor, trace and ultratrace quantitative and semiquantitative 

element analysis including B, P, and S, wWn linearity often over 4 orders of 

magnitude. 
Principle — Characteristic emissions from elements excited by an inductively 

coupled argon plasma have intensities proportional to concentrations. 
Limitations — Some spectral and scattered light interferences may come 

from the high concentrations of Fe and Mn in nodules. 
Ion chromatography: 
Application— Rapid quantitative determination of anions. Rapid cation 

determination for alkali and alkaline earth metals, NH4"' and 1st row 

transition elements. 
Principle — Ions separated by ion exchange techniques followed by ion 

electrical conductance proportional to the concentration of the specific ion. 
Limitations — Usually not applicable to anions with pKa >7. Most 2d and 3d 

row cations are determined with difficulty. 
Infrared spectroscopy: 
Application — Identification of compounds, amorphous and crystalline. 
Principle — Excitation of molecular vibrations by light absorption. 
Limitations — Medium sensitivity down to 1 to 2 pet. Broad absorption bands 

of OH group may overlap other spectral features in application to nodules. 

Neutron activation: 
Application — Trace and ultratrace elemental analysis of most elements 

including N, O, and F. 
Principle — Counting of radioactive species produced by neutron reactions. 
Limitations — The multielement nature of nodules present problems in 

spectral overlaps, which require chemical separation for some elements. 



Table 3. — Compound identification and elemental analysis methods for manganese nodule materials — Continued 



Optical microscopy: 
Application — Mineral or phase identification. 
Principle — Properties sucli as color, cleavage, refractive index, and 

characteristic crystal shapes using plane and polarized, transmitted, and 

reflected light systems. 
Limitations — Resolution limit is about 0.2 |xm but identification of particles 

<5 (xm is not practical, limiting the use of this technique for fine-grained 

nodule materials. 
Thermal analysis (TGA and DTA): 
Application — Qualitative and quantitative studies of materials including 

phase transitions, dehydration, reduction decomposition, crystallization, 

oxidation, and other heat-related properties. 
Principle — Changes in weight are measured as a function of Increased 

temperature over time. 
Limitations — Information is often empirical, and complementary analytical 

methods are needed to properly interpret data. 
Ultraviolet-visible spectrophotometry: 
Application — Quantitative analysis usually for final determination in 

chemical analysis schemes. 



Principle — Excitation of loosely bonded electrons with absorption of 

characteristic wavelength being proportional to the concentration of the 

compound. 
Limitations — Low specificity requiring chemical separation procedures prior 

to final determination. 
X-ray diffraction: 
Application — Identification of crystalline substances. 
Principle — Diffraction of X-rays from crystal planes providing "fingerprint" 

identification of crystalline materials. 
Limitations — Many nodule minerals are too fine grained or amorphous, 

making X-ray diffraction inapplicable. Generally not useful in the atomic 

number matrix of nodules for concentrations <5 wt pet. 
X-ray fluorescence spectrography: 
Application — Quantitative analysis of elements and semiquantitative 

survey of all elements of atomic number 1 1 or greater. 
Principle — X-ray excitation of characteristic X-rays. 
Limitations — Nonsensitive to elements of atomic numbers <1 1 (Na). Best 

sensitivity for heavier atomic number elements. 



against well-crystallized materials where mineralogy has been 
previously determined by XRD. Similar to XRD, direct IR is 
limited to compounds present at 2 to 5 pet or more in the 
sample. Other methods of compound identification such as 
optical microscopy, visual inspection, reflectivity, and other 



chemical and physical methods have definite applications. A 
combination of procedures is usually important to obtain reli- 
able compound identification on the macrocrystalline and micro- 
crystalline scale. A detailed description of over 50 minerals 
identified in manganese nodules is given in reference 1 6. 



CHEMICAL CHARACTERISTICS 



Elemental determination in manganese nodule processing 
reject waste material is amenable to several standard analyti- 
cal methods. (See table 3.) Interferences for 16 elements of 
interest in manganese nodule materials are listed in table 4 for 
four major instrumental analysis methods. Because of their 
importance in the determination of element concentrations in 
nodule materials, a brief discussion of each instrumental method 
listed in table 4 is given, followed by a brief discussion of ion 
chromatography for the determination of ions. 

ATOMIC ABSORPTION SPECTROPHOTOMETRY 

Atomic absorption spectrophotometric (AAS) techniques 
are readily adaptable for analysis of both the solid and liquid 
phases (75). In the liquid phase, direct flame, electrothermal, 
and hydride methods of AAS are applicable depending on the 
element and the concentration levels. Most elements are readily 
determined by flame AAS, but may require the use of electro- 
thermal AAS if the levels are below flame AAS detection limits. 
For As, Sb, and Se, either hydride or electrothermal AAS 
should be used. Specific methods or the use of a standard 
addition method may be required for some elements (24). 
Instrumental parameters and conditions for determining these 
elements can be found in the EPA manual, "Methods for 
Chemical Analysis of Water and Wastes" (32). 

For solid phase analysis (nodules or tailings), several 
multielement dissolution procedures are available. This report 
will address only three simple, rapid dissolution procedures. 
One method is used for the determination of the seven major 
and minor elements (Mn, Fe, Cu, Ni, Co, Pb, and Zn) and 
several trace elements (Cr, Tl, Cd, and Ba) by flame AAS. The 
other two dissolution procedures are used for determining 
trace elements by either electrothermal or hydride AAS. 

The dissolution procedure for determining the major, minor, 
and some trace elements in nodules and in the solid phase of 



the reject waste material uses HCI-HF acids with the resultant 
solution evaporated to dryness. This dried residue is then 
dissolved in 6A/ HCI, diluted to volume, and analyzed by flame 
AAS. 

Determination of the trace elements As, Sb, and Se by 
electrothermal or hydride AAS requires a separate dissolution 
procedure (73) to avoid analyte loss of the volatile compounds 
formed during evaporation of the solution and during the drying 
and charring stages prior to electrothermal atomization. The 
sample is dissolved in a HNO3-HF mixture with the addition of 
Ni(N03)2 and Mg(N03)2 as matrix modifiers. Additional trace 
elements that can be determined by electrothermal AAS are 
Ba, Cd, Cr, and Pb. 

High iron levels cause a spectral interference at the primary 
selenium wavelength of 196.0 nm (27). This spectral overlap 
problem can be solved by adjusting the pH of the solution to 3 
to 4 to precipitate the iron, with the selenium quantitatively 
carried on the Fe(0H)3 precipitate. This precipitate is sepa- 
rated and redissolved in 7N HCI and the solutions are ana- 
lyzed by hydride AAS to determine selenium. 

The selenium forms a hydride whereas iron does not react 
and therefore does not interfere. The use of polarized Zeeman- 
effect AAS on the original solution is a more direct way to 
eliminate the spectral interference caused by iron (79). This 
technique uses the magnetic portions of the selenium analyti- 
cal line, which facilitates the instrumental separation of iron 
and selenium spectral lines. 

A third dissolution procedure for the analysis of nodules and 
solid phase reject materials is a Parr^ bomb dissolution with 
aqua-regia-HF acid (28). All 16 elements are solubilized with- 
out loss and can be determined using flame AAS for the major 
and minor elements, and the remaining trace elements can be 
determined by flame, hydride, or electrothermal AAS. In deter- 



^Reference to specific products does not Imply endorsement by the Bureau of 
Mines. 



Table 4. — Sources of interference in elemental determination by quantitative instrumental methods 



Arsenic: 

AAS High Fe, Mn, and ottier metals will depress the sensitivity in 

hydride generation. Flame method gives poor sensitivity. 

ICP 2d-order spectral overlap from Ar. 

NAA Interference from Se, Ge, and Br. 

XRF Pb spectral interference at more sensitive Ka peak. Kp 

peak lacks sensitivity for quantities below 0.02 pet. 

Barium; 

AAS Ionization controlled by adding KCI. CaOH bands interfere. 

ICP None reported. 

NAA Interference from Ce and La. 

XRF None reported for quantities above 0.05 pet. 

Beryllium: 

AAS High Al, Mg, and Si will depress sensitivity. 

ICP 2d-order spectral overlap from Ar and OH band 

interference. 

NAA Not recommended. 

XRF Atomic number too low for XRF. 

Cadmium: 

AAS High Si interferes. 

ICP None reported. 

NAA Interference from Sn and from shielding. 

XRF None reported for quantities above 0.02 pet. 

Cobalt: 

AAS Some heavy metals and transition metals depress signal. 

ICP 2d-order spectral overlap from Ar. 

NAA Ni, Cu, and Fe cause enhancements. 

XRF Fe spectral interference below 0.01 pet. 

Chromium: 

AAS Fe, Ni, and PO/" depress the signal. 

ICP OH band interference. 

NAA Interference from Fe. 

XRF Enhanced by high iron. 

Copper: 

AAS None reported. 

ICP 2d-order spectral overlap from Ar. 

NAA Interference from Ni and Zn. 

XRF None reported for quantities above 0.005 pet. 

Iron: 

AAS Co, Cu, Ni, Si, and organic acids depress signal. 

ICP None reported. 

NAA Poor detectability from Co, Cr, Mn, and Ni. 

XRF None reported for quantities above 0.005 pet. 

Manganese: 

AAS Si depresses signal. High concentration of Fe enhances 

signal. 



ICP 2d-order spectral overlap from Ar and OH band 

interference. 

NAA Interference from Fe, Co. and Cr. 

XRF None reported for quantities above 0.005 pet. 

Molybdenum: 

AAS Cu, Fe, Sr, and S04^" depress the signal. 

ICP OH band interference. 

NAA Interference from Ru. 

XRF None reported for quantities above 0.02 pet. 

Nickel: 

AAS High Fe or Cr will enhance signal. 

ICP 1st order spectral overlap from Si. 

NAA Interference from Cu and Zn for Ni-64. No apparent 

interference for Ni-58. 
XRF None reported for quantities above 0.005 pet. 

Lead: 

AAS High Fe or other metals will enhance the signal. 

ICP 2d-order spectral overlap from H. 

NAA Interference from Bi. 

XRF None reported for quantities above 0.01 pet. 

Antimony: 
AAS Spectral interference from Cu and Pb. Depressed signal in 

high acidity. 
ICP 1st order spectral overlap from Si and 2d-order overlap 

from Ar. 

NAA Interference from Te and from self-shielding. 

XRF None reported for quantities above 0.02 pet. 

Selenium: 

AAS Some metals will depress the hydride generation signal. 

Flame absorbs signal. 

ICP None reported. * 

NAA Interference from Ge and Br. 

XRF None reported for quantities above 0.01 pet. 

Thallium: 

AAS None reported. 

ICP 1st order spectral overlap from Ar. 

NAA Interference from Pb and Hg. 

XRF None reported for quantities above 0.02 pet. 

Zinc: 

AAS High Cu, Fe, and Ni depress signal. 

ICP None reported. 

NAA Interference from Cu and Ni. 

XRF None reported for quantities above 0.005 pet. 



AAS 
ICP 



Atomic adsorption spectrophotometry. 
Inductively coupled plasma. 



NAA 
XRF 



Neutron activation analysis. 
X-ray diffraction. 



mining As, Sb, and Se by electrothermal AAS, matrix modifi- 
ers must be added to prevent losses during the drying and 
charring stages prior to atomization (73). 

Table 5 identifies each of the major elements as a major, 
minor, or trace component in manganese nodules, and gives 



suggested dissolution procedures and applicable methods for 
determination. For flame AAS conditions, relative error is gen- 
erally 2 to 5 pet of the actual value. At the very low levels 
determined by hydride or electrothermal AAS, the relative 
error is within 5 to 7 pet of the actual value. 



Table 5. — Sample dissolution and elemental analysis procedures for manganese nodule materials 



Element Concentration Dissolution procedure' 



Method of analysis^ 



Element Concentration 



Dissolution procedure' Method of analysis^ 

HCI-HF Flame AAS. 

HCI-HF Do. 

HCI-HF Do. 

HCI-HF Do. 

HCI-HF; Flame or electro- 

HN03-Ni(N03)2. thermal AAS. 

HN03-Ni(N03)2 Hydride or electro- 
thermal AAS. 

HN03-Ni(N03)2 Do. 

HCI-HF Flame AAS. 

HCI-HF Do. 



As Trace HN03-Ni(N03)2. . . 

Ba Minor HCI-HF; 

HN03-Ni(N03)2. 
Be Trace HCI-HF; 

HN03-Ni(N03)2. 
Cd do HCI-HF; 

HN03-Ni(N03)2. 

Co Minor HCI-HF 

Cr Trace HCI-HF; 

HN03-Ni(N03)2. 
Cu Major HCI-HF 



Hydride or electro- 
thermal AAS. 

Flame or electro- 
thermal AAS. 
Do. 

Do. 

Flame AAS. 
Flame or electro- 
thermal AAS. 
Flame AAS. 



Fe Major . 

Mn do. 

Mo Minor . 

Ni Major . 

Pb Minor . 



Sb 



Trace . 



Se do. 

Tl do. 

Zn Minor . 



' The Parr bomb dissolution procedure is suitable for all 16 elements. 

^ Inductively coupled plasma atomic emission spectroscopy is suitable for all 16 elements. 



INDUCTIVELY COUPLED PLASMA ATOMIC 
EMISSION SPECTROSCOPY 

The same sample preparation techniques used for atomic 
absorption are used for preparing solutions for the inductively 
coupled plasma (ICP) technique for multielement analysis by 
atomic emission spectroscopy. Atomic emission lends itself 
more readily to multielement analysis than does atomic 
absorption, and the interelement effects, self-absorption 
problems, and poor excitation of refractory elements, which 
create problems in conventional atomic emission spectroscopy, 
are greatly reduced in ICP. Spectral and interelement interfer- 
ences are a basic problem in any emission technique; however, 
interferences from background emission, flame gases, com- 
bustion products, and molecular species are greatly reduced 
in ICP. The few interferences that may cause problems in the 
analyses of manganese nodule materials are listed in table 4. 
The relative error in determining major, minor, and trace ele- 
ments in nodule materials by ICP is slightly higher compared 
with the 2 to 5 pet cited for AAS in the previous section. 

NEUTRON ACTIVATION ANALYSIS 

Neutron activation analysis (NAA) can provide concentra- 
tion values, especially on a trace level (< 0.001 pet), which 
might otherwise be impractical. However, a number of interfer- 
ences (18, 25) may create problems in measuring specific 
activities (see table 4). 

With materials such as manganese nodules, sensitivity and 
accuracy can be obtained in the measurement of the radioac- 
tive products from most of the elements only after chemical 
separation. The major types of counting interferences include 
the masking of trace element activities by the much greater 
activities of one or more other elements because of amounts, 
cross sections, or long half-lives, and the occurence of similar 
gamma-ray photopeaks or B" emissions that are not conve- 
niently resolved (for example, Fe-59 and Co-60). Postirradia- 
tion separations are preferred over preirradiation because no 
reagent blank is involved and the postirradiation separation 
need not be quantitative in many cases to obtain quantitative 
results. The chemical separations, whether performed before 
or after irradiation, follow conventional methods except for 
added precautions in working with the radioactive samples. A 
procedure using chemical separations for the determination of 
42 elements in lunar material (5) would appear to require very 
little modification to provide good results for manganese nod- 
ule materials. 



X-RAY FLUORESCENCE SPECTROGRAPHY 

The application of X-ray fluorescence (XRF) spectrography 
to manganese nodule and reject waste materials involves 
conventional methods of XRF analysis with corrections for 
peak overlap and enhancement and depression effects. The 
wavelength- and energy-dispersive methods of XRF are appli- 
cable for Co, Cu, Fe, Mn, Ni, Zn, and Pb where these elements 
are major or minor constituents of the solid phase (nodules or 
tailings). The remaining elements of interest for this report are 
at levels not usually detectable by direct XRF methods. A good 
general reference on XRF analysis is Bertin (4). 

Sample preparation of nodules or tailings for XRF analysis 
requires drying to remove moisture, followed by one of two 
methods of sample preparation: pressed pellets or fused disks. 
To prepare pressed pellets, the dry weighed sample is mixed 
with a binder and pressed into a pellet at -1 5 tons per square 



inch pressure. These pellets are then analyzed and compared 
with standards of known composition for the elements of interest. 
The second sample preparation procedure, fused disks, requires 
a dry weighed sample to be mixed with a glass-forming low- 
atomic number material, followed by fusion at high tempera- 
ture (-' 800°-1 ,200° C). This method eliminates particle size 
problems and reduces matrix effects. However, sensitivity is 
decreased because of dilution of the sample by the glass- 
forming material. The dilution is usually about six parts flux to 
one part sample in fusions compared with pressed pellets 
where 85 pet of the final pellet is sample. This loss of sensitivity 
by using fused disks may pose a problem if concentrations of 
the element of interest are already low. 

Major and minor elements can be determined by XRF pro- 
vided that adequate primary and secondary standards can be 
obtained and/or made for the elements of interest in an appro- 
priate matrix. The precision of analysis will vary from ± 1 pet of 
the amount present for the major elements (>5 pet) such as 
manganese and iron, and ranges up to ± 20 pet of the concen- 
tration present for elements in the very low (<0.1 pet) range. 
This relative error is also very dependent on atomic number in 
the lower concentration range, with the greater problems occur- 
ring with the lower atomic number elements. Applications of 
XRF to nodule analysis has been reported (70, 12), giving 
X-ray values in good agreement with atomic absorption analy- 
ses of nodules (11). 



ION CHROMATOGRAPHY 

Conventional, standard wet chemical, and colorimetric meth- 
ods for chloride, fluoride, nitrate, ammonium, phosphate, and 
sulfate are available (32). In order to determine five anions 
of interest in the manganese nodule materials using the con- 
ventional methods, a separate sample would be required for 
each anion determination. Since the introduction of ion chro- 
matography (IC) (29), this multi-ion method has been used to 
determine many anions and cations in a variety of environmen- 
tal and geological matrices (14, 20, 26-27). 

In the liquid phases from processing nodules, NH4*, CI', 
S04^", and COa^" can be determined by sample dilution followed 
by injection into the IC. Table 6 summarizes the operating 
conditions for determining six anions and one cation of interest. 
The six anions, F, CI", NO3", P04^", S04^", and COa^" can be 
determined in less than 20 min on one sample using one set of 
conditions. The ammonium ion can be determined in a separ- 
ate sample of the liquid fraction using another set of IC con- 
ditions (20). 

For liquid samples, IC methods for determining carbonate 
(COa^) depend on concentration. At >500-pg/mL levels, the 
parameters outlined in table 6 are adequate. For <500-^g/mL 
levels, a separate method, called ion exclusion is required. In 
ion exclusion only a suppressor column is required and dis- 
tilled water is used as the eluent; this procedure is applicable 
down to the l-pg/mL level. 

Transition metal ions such as Fe^^ tie up active sites in the 
resins used in IC, effectively "poisoning" the resin. This prob- 
lem is resolved by inserting a small precolumn in the system. 
The transition ions remain in the precolumn without affecting 
the separator's column efficiency. The precolumn is periodi- 
cally replaced to prevent carryover to the separator column. 

Acid dissolution of solids is not practical because the acid or 
combination of acids used in the dissolution will prevent the 
determination of the acid anions in the original sample. By 
fusing the sample with Na2C03 and leaching with deionized 
water, the anions in the sample are converted to the water 



Table 6. — Ion chromatograph operating conditions for 
determining anions and NH4' 





Elution 




Detection 




time' 


Possible 


limits, 


Constituent 


min 


interferences 


M-g/mL 


Chloride (Cr) 


=4 


HighCOa^- 
(>1,000ji.g/mL). 


0.5 


Fluoride (F') 


-1.5 


None expected 


.2 


Nitrate (NO3-) 


-9 


High P04^- 
(>100tJLg/mL). 


1.0 


Phosphate 


=7 


High NO3" 


1.0 


(P04^-). 




(>100 M-g/mL). 




Sulfate 


-15 


None expected 


1.0 


(S04=-). 








Carbonate 


-3 


Higher 


^500.0 


(CO32-). 




(>50 |i,g/mL). 




Ammonium 


-16 


High Na 


5.0 


(NH4*). 




(>100|jLg/mL). 





' All elution times are based on using a 0.003/W NaHCO3/0.0024W NajCOj 
eluent and a 3- by 500-mm anion separator column for all except ammonium 
(0.005/W HNO3 eluent and a 6- by 250-mm cation separator) at a flow rate of 
2.5 mL/min. 

^ A limit of ~1 |oLg/mL can be detected by use of ion exclusion using 
distilled H2O as an eluent and the suppressor column only. 



soluble Na^ form. This fusion technique has the additional 
advantage of forming transition metal carbonates that gener- 
ally remain insoluble, thereby eliminating the transition metal 
poisoning of the column. After the samples are fused and 
water leached, the liquid is injected into the IC for analysis. A 



Bureau of Mines developed fusion technique was applied 
successfully to the anion IC characterization of phosphate 
minerals (14) and cement kiln dust (20). 

The carbonate ion in the solid phase cannot be analyzed by 
IC using the fusion method because of the COa^' contribution 
from the flux. Thermal gravimetric analysis of the unfused 
solid allows the determination of COa^" concentration based on 
the thermal evolution of CO2 coupled with gas chromatograpy. 
The evolution of CO2 by acid with subsequent capture of CO2 
could also be applicable. 

Detection limits for the various ions by IC are given in table 
6. The IC method is generally within ±5 pet relative of the 
actual value depending on the concentration of the ions of 
interest. 



WET CHEMICAL METHODS 

Classical wet chemical methods of analysis are available for 
use in determining individual elements and ionic species of 
interest, but they are generally time consuming and require a 
separate sample for each determination. Various standard 
analytical methods are listed by EPA (32) including titrimetric, 
gravimetric, spectrophotometric, potentiometric, and specific 
ion electrode methods in addition to specific parameter meth- 
ods such as chemical oxygen demand (COD) and pH. The 
focus of this report is on the use of multielement techniques 
however, and no detailed discussion will be made of these 
single constituent analytical methods. 



COMPARISON OF CHEMICAL ANALYSIS RESULTS 



Several nodule materials were used for interlaboratory com- 
parisons of analytical methods. Seven manganese nodule 
standards were received, five were in-house standards from 
two industrial laboratories (A and B) and the other two were 
available from the U.S. Geological Survey (USGS) (7 1). Ana- 
lytical results from laboratories A and B and the two USGS 



standards are compared with results obtained by the Bureau's 
Avondale (MD) Research Center in table 7. 

Both industrial laboratories had obtained their data using 
AASforthe elemental determinations, although different disso- 
lution procedures were used. USGS published data are based 
on average results reported by various laboratories by several 



Table 7. — Comparison of interlaboratory analyses of manganese nodule standards 



Standard 



Micrograms per gram 



As 



Be 



Cd 



Cr 



Pb 



Sb 



Se 



Weight percent 



Ba 



Co 



Cu 



Fe 



Mn 



Mo 



Ni 



Zn 



A-1;' 

Lab A ... . 

BOM 

A-2:' 

Lab A ... . 

BOM 

A-3:' 

Lab A ... . 

BOM 

B-1:' 

Lab B ... . 

BOM 

B-2:' 

Lab B ... . 

BOM 

USGS A-1 :2 

USGS.... 

BOM 

USGSP-1:2 

USGS.... 

BOM 



ND 
ND 

ND 
ND 

ND 
ND 

ND 
48 

ND 
73 

298 
306 

39 
45 



ND 
ND 

ND 
<20 

ND 
<20 

2 
3 

2 
2 

6 
ND 

3 
4 



ND 
ND 



ND 
21 



ND 
20 



ND 
14 



ND 
20 



6.5 
8.0 



22 
22 



ND 
ND 

ND 
30 

ND 
30 

ND 
60 

ND 
50 

24 
30 

17.5 
15 



ND 
ND 

ND 
490 

ND 
400 

480 
450 

490 
455 

846 
860 

555 
495 



ND 
ND 

ND 
ND 

ND 
ND 

ND 

41 

ND 
57 

34 
25 

50 
44 



ND 
ND 

ND 
ND 

ND 
ND 

ND 
ND 

ND 
ND 

ND 
<0.26 

ND 
<0.26 



ND 
ND 

ND 
220 

ND 
180 

ND 
190 

ND 
230 

61 
ND 

154 
150 



ND 
ND 

ND 
0.14 

ND 
.15 

.26 
.26 

.25 
.25 

.17 
.19 

.34 
.31 



0.24 
.22 

.25 
.25 

.24 
.24 

.22 

.24 

.26 
.25 

.31 
.31 

.22 

.24 



0.97 
1.00 

1.23 
1.18 

1.28 
1.28 

1.01 
1.00 

1.30 
1.27 

.11 
.12 

1.15 
1,17 



7.3 
7.0 

6.4 
6.2 

5.0 
4.8 

6.8 
6.4 

5.9 
5.7 

10.9 
11.3 

5.8 
6.1 



24.2 
23.4 

29.8 
28.4 

34.0 
32.2 

26.7 
26.6 

31.4 
31.8 

18.5 
20.0 

29.1 
29.9 



ND 
ND 

ND 
ND 

ND 
ND 

0.05 
.06 

.06 
.05 

.04 
ND 

.08 
.07 



1.19 
1.15 

1.46 
1.40 

1.26 
1.24 

1.36 
1.33 

1.55 
1.51 

.64 
.69 

1.34 
1.36 



0.10 
.09 



BOM Bureau of Mines. ND Not determined. USGS U.S. Geological Survey. 

' Industrial laboratory in-house reference standard. ^ See reference 11 for information on the USGS reference sample. 



Table 8. — Round-robin results for Cuprlon process reject waste 
material, solid phase 



Element 



As . 
Be. 
Cd. 
Cr . 
Mo. 
Pb. 
Sb. 
Se. 
Tl.. 



Bureau of Mines 



SLCRC AIRC 



RRC 



AvRC 



Industrial 



LabB 



CONCENTRATION, ixg/g 



AIRC Albany (OR) Research Center. 

AvRC Avondale (MD) Research Center. 

ND Not determined. 

RRC Reno (NV) Research Center. 

SLCRC Salt Lake City (UT) Research Center. 



LabC 







CONCENTRATION, 


wt pet 






Ba 


0.26 


0.33 


0.54 


0.24 


0.29 


ND 


Co 


.17 


.17 


.19 


.18 


.17 


0.18 


Cu 


.14 


.14 


.13 


.14 


.15 


.12 


Fe 


5.5 


7.8 


4.8 


5.8 


5.6 


6.4 


Mn 


26.0 


27.4 


25.8 


27.0 


27.8 


32.2 


Ni 


.20 


.21 


.32 


.22 


.20 


.28 


Zn 


.11 


.12 


<.01 


.13 


,11 


.11 



45 


46 


<40 


49 


ND 


ND 


ND 


2 


<3 


ND 


40 


30 


21 


20 


19 


29 


56 


<500 


30 


21 


50 


ND 


28 


68 


<100 


590 


650 


540 


500 


600 


<10 


24 


72 


40 


ND 


<1 


<5 


ND 


ND 


ND 


150 


<10 


ND 


83 


ND 



55 
ND 

49 
ND 
190 
410 

38 

1 

160 



Table 9. — Round-robin results for Cuprion process reject waste 
material, liquid phase, micrograms per milliliter 



Elsmsnt 


Bureau of Mines 


Industrial 




SLCRC 


AIRC 


RRC 


AvRC 


labC 


As 


0.015 


0.01 


<0.03 


0.018 


0.025 


Ba 


.16 


.11 


.17 


<.8 


.27 


Be 


ND 


ND 


.003 


<.03 


<.01 


Cd 


<.01 


<.05 


<.004 


<.03 


<.05 


Co 


<.01 


<.1 


<.2 


<.3 


.10 ■ 


Cr 


<.1 


.3 


<.04 


<.2 


<.1 


Cu 


.15 
<.01 
<.1 


<.10 
<.20 
<.1 


<.50 
<.20 
<.03 


<.11 
<.50 
<.7 


< 05 


Fe 


<.05 


Mn 


<.02 


Mo 


14 


ND 


15 


30 


63 


Ni 


<.01 


<.10 


<.03 


<.10 


<.20 


Pb 


<.1 
<.01 
.02 


<.5 

<.01 

<.02 


<.06 
<.02 

.16 


<.2 

.007 
.02 


<.01 


Sb 


<.018 


Se 


<.03 


Tl 


.4 


<.1 


ND 


<.2 


.11 


Zn 


<.1 


<.1 


3.3 


<.03 


<.04 



AIRC Albany (OR) Research Center. 

AvRC Avondale (MD) Research Center. 

ND Not determined. 

RRC Reno (NV) Research Center. 

SLCRC Salt Lake City (UT) Research Center. 



methods (7 7). The Avondale results were obtained from the 
HCI-HF and the HNO3-HF dissolution procedures. Results 
obtained by AAS by Avondale personnel agree well with results 
reported by the industrial laboratories and the USGS. 

A reject waste slurry material from the Cuprion process was 
prepared, blended, and samples were sent to the Bureau's 
Salt Lake City (UT), Albany (OR), Reno (NV), and Avondale 
(MD) Research Centers and to two independent industrial 
laboratories (B and C). Analytical data were requested for the 
1 6 elements of interest, as well as any other element or ionic 
species they could conveniently determine. Analyses of both 
the liquid and solid phases were performed by all laboratories 
except industrial laboratory B, which reported only the solid 
phase analysis. Table 8 gives the results obtained by the six 
laboratories for the solid phase. Good agreement was obtained 
for the major and minor elements; Co, Cu, Ni, and Zn, and the 



trace elements; As, Be, Cr, Pb, and Se. The elements Ba, Fe, 
Cd, Mn, Mo, Sb, and Tl had only moderate agreement. It 
should be noted that the Avondale laboratory and industrial 
laboratory B have more experience in analyzing nodules and 
nodule waste materials than the other four laboratories. However, 
agreement overall can be considered acceptable for this initial 
round robin. 

Table 9 gives the round-robin results for the liquid phase of 
the tested material. Again agreement for most of the elements 
provides confidence in the analytical methods used. 

The results for both phases of the tested material and the 
manganese nodule standards indicate that standard dissolu- 
tion procedures listed in this report for nodules as well as 
procedures used in laboratories accustomed to analyzing inor- 
ganic matrices are adequate for determining the elemental 
content of nodules and reject waste materials. 



LEACHING TESTS 



EP TOXICITY TEST 

According to EPA regulations under the Resource Conser- 
vation and Recovery Act (RCRA) (37), a solid waste must be 
listed as a hazardous waste if it exhibits any of the following 
characteristics as defined in RCRA: ignitability, corrosivity, 
reactivity, and/or extraction procedure (EP) toxicity (8-9). 

Reject waste materials from manganese nodule processing 
will not exhibit any properties of ignitability or reactivity. Corrosivity 
applies primarily to liquid wastes and should not be a problem 
if adequate waste management practices are used in the 
washing of the tailings. 

The only applicable hazardous waste criterion is the EP 
toxicity test. Briefly, the EP toxicity test consists of agitating, 
for 24 h, a minimum sample weight of 1 00 g of filtered material 
in 1 ,600 mL of distilled water (maintain a 16:1 water-to-solids 
ratio for larger sample weights) to which a maximum of 400 mL 
of 0.5N acetic acid (4 mL of acid per gram of material) may be 



added to maintain a pH of 5.0 ± 0.2. If all 400 mL of the acid is 
not required to achieve the desired pH, the remaining volume 
to make 2,000 mL (20:1 liquid-to-solid ratio) is added as dis- 
tilled water. The solution is filtered on a 0.45-pm pore size 
filter. The resulting extract (liquid portion) in the EP toxicity test 
is not to exceed 100 times the National Drinking Water Stan- 
dard for concentrations of eight metals: Ag, As, Ba, Cd, Cr, Hg, 
Pb, and Se. The EP toxicity limits, in micrograms per milliliter, 
are as follows: Ag, 5; As, 5; Ba, 1 00; Cd, 1 ; Cr, 5; Hg, 0.2; Pb, 5; 
and Se, 1 . 



ASTM SHAKE EXTRACTION TEST 

A second leaching test, the American Society for Testing 
Materials (ASTM) shake extraction test (2), has been pro- 
posed by ASTM as an alternate method for evaluating wastes, 
especially those of low organic content such as mining waste. 



This test consists of contacting a minimum of 350 g of dried 
material with distilled deionized water; the weight of water to 
be four times the sample weight. The slurry is agitated in a 
closed container for 48 h and the liquid portion filtered on 
0.45-^im filter paper. The extract is then analyzed for the 
desired components including those outlined in the RCRA 
criteria. 

U.S. ARMY CORPS OF ENGINEERS 
SEAWATER ELUTRIANT TEST 

In the possible case of ocean disposal of nodule reject 
waste materials, either by ocean dumping or by ocean outfalls, 
a seawater leachate test may provide more appropriate data 
than the previous two leach tests. The Corps of Engineers 
dredge material elutriant test can be used to evaluate the 
extent of seawater-leachable metals in the waste materials 
{33). The procedure consists of mixing a weighed volume of 
material with four times the volume of seawater, agitating for 1 
h, filtering and analyzing the seawater solution. Concentra- 
tions are compared with those in the seawater prior to leaching. 
Based on this analysis, concentrations of the elements at 
proposed mixing levels found in ocean outfalls or in ocean 
dumping can be extrapolated. Depending on final regulations 
in regard to ocean disposal, the degree of mixing required can 
be regulated by either dumping large amounts at once for 
minimal mixing rates or by trickling to provide for high mixing 
rates. NOAA has an ongoing study to establish requirements 
in this area. 

RESULTS OF LEACHING TESTS 

The EP toxicity test, the ASTM shake extraction test, and 
the Corps of Engineers seawater elutriant test were all applied 
to the Cuprion pilot plant tailings described in table 8. The 
results are listed in table 1 0. Comparison of the established 



Table 10. — Element concentration in leachate from leaching 
tests on Cuprion process reject waste material, 
micrograms per milliliter 



Element 


EP toxicity 
test 


ASTM shake ex- 
traction test 


Seawater elu- 
triant test 


Ag 

As 

Ba 

Be 

Cd 

Co 

Cr 

Cu 

Fe 

Hg 

Mn 

Mo 

Ni 

Pb 

Sb 

Se 

Tl 

Zn 


<0.07 

.004 
<2 
<.06 
.06 
12 
<.4 
1.3 
<.5 
.019 
1,690 
<.6 
9.9 
<.7 

.003 
<.003 
<2 
2.5 


<0.07 

<.003 
<2 

<.06 

<.05 

<.3 

<.4 

<.2 

<.5 

ND 

<.06 

3.8 

<.1 

<.7 

<.003 

<.003 
<2 

<.02 


<0.07 

<.003 
<2 
<.06 

<.05 

<.3 

<.4 

<.2 

<.5 

ND 
.28 

<.6 

<.10 

<.7 

<.003 

<.003 
<2 

<.04 



ND Not determined. 



NOTE. — EP toxicity test has the following maximum allowable concentration 
of contaminants for 8 elements, in micrograms per milliliter: Ag, 5; As, 5; Ba, 
100; Cd, 1 ; Cr, 5; Hg, 0.2; Pb, 5; and Se, 1 . 



EP toxicity test limits listed in table 1 with the concentrations 
leached from the Cuprion pilot plant rejects show that leachate 
concentrations from this waste material are consistently one 
to three orders of magnitude lower than would be required to 
be classified as hazardous. Manganese, cobalt, and nickel 
were leached from the rejects to some extent by the EP toxicity 
test but none of these are considered in the hazardous waste 
criteria. 



CONCLUSIONS 



In general, the conventional physical and chemical analyti- 
cal procedures used by laboratories experienced in working 
with inorganic matrices are applicable to manganese nodules 
and their processing reject waste materials. The high iron and 
manganese content of nodule materials must be taken into 
account in chemical analyses, especially for possible interfer- 
ences in trace element determinations. The precautions are 
described or referenced in the text for each of the various 
methods discussed. 

The fine-grained or amorphous nature of manganese nod- 
ules and nodule tailings generally limit the identification of 
mineral compounds to the major and minor constituents such 
as manganese carbonate or oxide, quartz, feldspars, and 
clays. The use of referenced electron microscopic techniques 
is purported to identify minerals in concentrations less than 
about 5 wt pet. The iron compounds are often amorphous, 
requiring the use of referenced infrared spectroscopy or chemi- 
cal methods for identification. 



In comparisons of leachate tests on Cuprion pilot-plant tailings, 
the EP toxicity test seemed to show greater leaching ability for 
the eight regulated elements than the ASTM shake extraction 
test or the Corps of Engineers seawater elutriant test. However, 
these levels were one to three orders of magnitude lower than 
would be required for the wastes to be classified as hazardous. 
Three elements not listed in classifying a waste as hazardous, 
Mn, Co, and Ni, showed some leachability, but the leaching 
was minimal. 

The procedures described in this report are not being sug- 
gested as standard methods, but are simply a review of state- 
of-the-science analytical techniques as applied to manganese 
nodule materials. Any skilled inorganic analyst taking the pre- 
cautions described in this report for the interferences should 
be capable of providing reliable analyses of manganese nod- 
ules and nodule processing reject waste materials. 



10 



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31 . U.S. Congress. Resource Conservation and Recovery Act of 
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MS, July 1977, 103 pp. 



•CiU.S. GOVERNMENT PRINTING OFFICE: 1983-605-015/63 



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